Neutral development of bordeaux citazols in the presence of dinitro-benzene-sulfonicacids



'ni ted tates Patent Patented Oct. 11, 1960 arise NEUTRAL DEVELOPMENT OF BORDEAUX CITA- ZOLS IN THE PRESENCE OF DINITRO-BEN- ZENE-SULFONIC ACIDS Ermanno Gaetani, Milan, Italy, assignor to Aziende (gala-Ii Nazionali Aifini-ACNA-S.p.A., a corporation y No Drawing. Filed Apr. 1'3, 1959, Ser. No. 805,681 Claims priority, application Italy Apr. 15, 1958 10 Claims. (Cl. 8-71) and coupling components, i.e. naphthols. They are usually called ice dyes.

Whenever similar mixtures are applied to the textile fiber, the dye is developed by treatment either in acid bath or by neutral or acid steaming in the presence, however, of hydroxy-amiues, which in this case substitute for the fixed alkalis generally used for dissolving the coupling naphthols.

In more recent times mixtures as mentioned above, ie triazenes plus coupling components, have appeared which are capable of developing the dye even by only neutral steaming in the presence of fixed alkalis. Although the advantages reliably obtained from said neutral steaming process have led to a favorable attitude towards these mixtures, it was however noted, in certain instances, that during the neutral development, with neutral steam, but in alkaline medium, certain deficiencies become very prominent which had also been revealed at times in the previously used methods employing either acid or neutral steaming in the presence of hydroxy-amines. Said mixtures are sensitive, to a varying degree depending upon the components, to the means of reduction; and all the more so if the development takes place in alkaline medium.

This reducing effect can also be caused, in the absence of other means, by the action of the cellulose itself (i.e. of both fibers and thickener) due to an initial degradation thereof in the presence of alkalis.

Consequently, in all formulations of prints in which tn'azene and naphthol mixtures are employed for development by neutral steaming, components are included to protect the dye against these undesirable reductions that cause weakening of the shade and decrease in yield. These substances are, for example, sodium chlorate, sodium chromate and sodium m-nitro benzene-sulfonate of the Formula A,

SO Na All of these substances, to a varying degree, have oxidizing properties.

While in most cases good results are achieved by adding the said substances to the printing paste, it was noted that the oxidizing substances mentioned will not be sufficient if the triazene consists of certain nitroamines.

During the neutral steaming a very extensive alteration of the nitroamine molecule takes place, so that much more turbid and less deep shades are obtained the longer the steaming action is carried out and the higher the temperature employed for the purpose of achieving full color development.

These amines, which are normal'triazene components 5 for this type of dye, are for instance 5-nitro-2-aminotoluol (B), 5-nitro-2-aminoanisol (C) and 3-nitro-2-aminoanisol (D),

0 CH3 0 CH;

C'Ha

NH; NH, NH:

NO NO NO;

These components contain the nitro group in para or ortho position to the diazo-amino group; whereas on the contrary other nitroamines like 4-nitro-2-aminotoluol (E) and 4-nitro-2-aminoanisol (F), of the formulae CH3 0 CH3 NH: N Hz N0 NO:

the nitric group of which is found in meta position to the amine group, afford triazenes which behave Wholly normally during the development in admixture with couplings or coupling components in the presence of the normal oxidizing substances already mentioned.

We have now found, and it is the object of the present invention that, surprisingly, the use of moderate amounts of aromatic polynitrate products in the printing pastes containing nitroamirie triazenes (of a formula equal or similar to Formulae B, C, and D) permits the hindering of the reducing effect upon nitroamine and results in obtaining the development of pure shades of the corresponding dye.

These poly-nitro compounds are, for instance, sodium- 2-4-dinitro-benzene sulfonate (G), sodium 3-5-dintrobenzene-sulfonate (H) and sodium -2-6-dintro-4-chloroenzene-sulfonate (I).

SIOaNQ SO3Na SOzNa.

NO: NO NO:

NO NO:

and other alkaline or alkaline earth metal salts. A most surprising fact about the effect of these dinitro derivatives is that the effect seems to occur in a quite different way than the mode of action of the oxidizing substances generally used in the printing pastes already indicated.

It was in fact observed that:

-(1) The use of sodium chromate even in considerable excess in comparison with the normal amounts (sodium chromate being a much more powerful oxidant so that it is generally recommended whenever a more pronounced action than that of sodium mono-nitro-benzene-sulfonate is desired), shows none of the desired effect. That is, it does not avoid formation of turbid but less intense shades. 0n the contrary, it has an unfavorable influence upon the shade.

(2) For instance, the use of m-nitro-benzene-sulfonate in ratios even more than triple in comparison with dinitrobenzene-sulfonate, has an effect which is slightly better than that of chromate but clearly less than the effect of the dinitro compound.

It is therefore not merely a question as to the quantity of nitric groups present, or of the amount of oxidant;

indeed apparently the specific action characteristic of the compounds mentioned is involved.

Saiddinitrocompounds maybe added to the printing pastes prior to or after introducing the mixture of'tria'zene with its coupling naphthol compound or also owing to the moderate employment percentage of these compounds, they may be added in the dry state to the same mixture to substitute, Wholly or partially, for the usual blending with inert substances, for example sodium sulfate or other inorganic salts.

To complete and illustrate what has been stated above, a numberof examples of the application and development of mixtures consisting of triazene with coupling components are given below. It should be understood that neither the products nor the'quantities indicated are intended to limit the scope of this invention.

Example 1 The dye consists of a nearly equimolecular mixture of a coupling compound or component with the triazene.

The coupling compound is the ortho-toluidide of the beta-hydroxy-naphthoic acid. The triazene is formed by action of the diazo compound of S-nitro-Z-aminotoluene (Formula B) acting upon the sodium salt of N- alkyl-S-(or 4)-sulfo-anthranilic acid (where alkyl is ethyl, isopropyl etc.) or upon sodium cyanamide.

The mixture is appropriately blended with inert inorganic salts so that 100 parts of dye contain about 0.08 gr./mol. of reacting compounds.

With this dye a printing paste of the following composition is prepared: 60 g. dye are kneaded with 50 g. denatured alcohol and 13 .gr. of 36 B; caustic soda; the mixture thus' obtained is then diluted with 200 g. water to which 627 g. tragacanth gum thickener and 50 g. neutral chromate solution are added; total=1000 g.

The neutral chromate solution is prepared by dissolving: 150 g. sodium bichromate in 700 g. waterand in 150 g. 36 B. caustic soda; total, 1000 g. i

m The printing paste thus obtained is then printed upon cotton cloth which is acid 'or neutral steamed for 3, 6, 9

to 20 minutes. Whereas in the first case, i.e. acid steammg, a bright Bordeaux shade will be achieved, in the second case a slightly more turbid and considerably less intense shade after steaming for 3 minutes will be observed. Prolonged steaming will cause' an increasingly turbid and bluish shade. V

If the quantity of chromatesolution in the above paste is doubled (100 parts), the result during dye development does not change or improve but will become slightly worse.

Example 2 It in the printing paste described in Example 1, instead of 18 parts of thickener an identical amount is added of sodium-2-4-dinitro-benzene-sulfonate (Formula G, molecular weight 270, 18 g.=0.0666 g./mol), after prmting and neutral development (groups NO =0.1332

g./mol) a considerably purer (not bluish) and limpid Bordeaux color will be obtained that is even remarkably purer after prolonged steaming.

If, however, instead of 2-4-dinitro compound an identical quantity of sodium 3-5-dinitro-ber1ene-sulfonate isomer (Formula H) is used, the result will be identical with that obtained when 2-4-dinitro compound is introduced.

' Example 3 the printing paste described in Example 1, the 18 parts of thickener are replaced with an identical amount of sodium 3-nitro-benzene-sulfonate (Formula A, molecular weight 225, 18 g.=0.08 g./mol, groups NO =0.O8 g./mol), after printing and neutral development a slight improvement in purity and shade will be noted in comparison with the results which are obtained when this auxiliary is not used; however, this improvement lies considerably below the results that are achieved when 'No =0.042 g./mol),

'iary is not used. However,

employing the auxiliary dinitro-benzol-sulfonates illustrated in Example 2.

If the amount of sodium mono-triazene-sulfonate is more than tripled (60 instead of 18 parts or 0.267 g./mol, groups NO =0.267) the result will not be much different than if 18 parts were used, although the nitric groups would then be 0.267 g./mol, i.e. double the quantity used as in Example 2.

Example 4 If in the printing paste described in Example 1, instead of 18 to 50 parts of thickener an identical amount is added of sodium benzene-sulfonate, no improvement will be noted in comparison with the results obtained in Example 1 after printing and neutral development.

The same occurs if benzene sulfonate is replaced by an aliphatic nitro derivative such as guanidine or by an inorganic salt such as sodium nitrite.

Example .5

As in Example 1, the dye consists of a nearly equimolecular mixture of a coupling with a triazene, the coupling being the alpha-naphthylamide of beta-hydroxynaphthoic acid. a

The triazene is formed by diazo-S-nitro-Z-aminoanisol (Formula C) acting upon the sodium salt of N- isopropyl-5-- or 4 sulfo-anthranilic acid or upon the N- ethyl, or N-methyl compound, or on sodium cyanamide. The mixture is suitably blended with inert inorganic salts so that parts of the dye contains about 0.075 g./mol reacting compound.

With the aid of this dye a printing paste is prepared which may be set up under identical conditions and at equal quantities used in preparing the paste of Example 1.

The paste thus obtained is then printed upon cotton fabric which is then steamed either in acid or in neutral medium for 3, 6, 9 to 20 minutes. Whereas in the first case an' intense Bordeaux shade is obtained, the shade becomes more and more turbid and bluish when processing with neutral steaming.

Example 6 If in the printing paste describedin Example 5, instead of 9.5 parts of thickener an identical amount is placed of sodium m-nitro-benzene-sulfonate (Formula A, 225 molecular weight, 9.5. g.=0.042 g./mol; groups after printing and neutral development a certain improvement is noted as to purity and shade in respect of the results obtained when this auxilthis improvement will still lie below the results that are obtained by applying the dinitro-benzene-sulfonic compounds illustrated in Example 6, particularly after prolonged steaming.

If the amount of sodium mono-nitrobenzene-sulfonate is more than tripled (36 g. instead of 9.5 g., about 0.16 g./mol instead of 0.042 and groups NO =0.16), the result is not difierent from that obtained when only 9.5 parts were used, although the nitric groups then avail- 0.16 g./mol, i.e. more than double the Example 8 No particular improvement is noted from introducing into the printing paste described in Example 5, a nitro-aliphatic derivative (such 'asnitro'guanidin) or inorganic di m nit e- Example 9 Instead of preparing a printing paste containing the triazene-coupling mixture and then adding sodium 2-4 or 3-5-dinitro-benzene-sulfonate either in the solid state or mixed or dissolved With an appropriate solvent already employed to prepare the paste (ethyl glycol or one of its ethers or an ethanolamine), dry sodium dinitro-sulfonate may also be mixed with the triazene and the coupling naphthol. The mixture thus obtained may be stored indefinitely, and may be used for the preparation of the printing paste when required.

I claim:

1. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising an oxidizing agent, a printing paste triazene compound, and a naphthol coupling component, the improvement comprising steaming the textile in the presence of a compound taken from the class consisting of dinitro-benzene-sulfonic acid salts of alkali and alkaline earth metals, the two nitro groups of which are on non-adjacent carbon atoms.

2. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising sodium chromate, a printing paste triazene compound, and a naphthol azo dye coupling component, the improvement comprising steaming the textile in the presence of a compound taken from the class consisting of dinitro-benzene-sulfonic acid salts of alkali and alkaline earth metals, the two nitro groups of which are on non-adjacent carbon atoms.

3. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising a chromate, a printing paste triazene compound, and a naphthol coupling component, the improvement comprising steaming the textile in the presence of a member of the group consisting of alkali and alkaline earth metal salts of a compound taken from the class consisting of 3,5-dinitrobenzene-sulfonic acid, 2,4-dinitro-benzene-sulfonic acid, and 2,6-dinitro-benzene-sulfonic acid.

4. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising a chromate oxidizing agent, a naphthol coupling component, and a triazene formed by reacting a diazo compound of a member of the group consisting of 5-nitro-2-aminotoluol, 5-nitro-2-aminoanisol, and 3-nitro-2-aminoanisol with an alkali metal salt of a member of the group consisting of an N-lower alkyl-sulfoanthranilic acid and cyanamide, the improvement comprising steaming the textile in the presence of a member of the group consisting of alkali, and alkaline earth metal salts of a compound taken from the class consisting of 3,5-dinitro-benzene-sulionic acid, 2,4-dinitro-benzene-sulfonic acid, and 2,6-dinitro-benzene-sulfonic acid.

5. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising sodium chromate, ortho-toluidide of beta-hydroxy naphthoic acid, and a triazene formed by reacting a diazo compound of a member of the group consisting of S-nitro-Z-aminotoluol, 5-nitro-2-aminoanisol, and 3-nitro-2-aminoam'sol with a sodium metal salt of a member of .the group con sisting of an N-lower ialkyl-sulfoanthranilic acid and cyanamide, the improvement comprising steaming the textile in the presence of a member of the group consisting of alkali and alkaline earth metal salts of a compound taken from the class consisting of 3,5-dinitro-tbenzene-sulfonic acid, 2,4-dinitro-benzene-sulfonic acid, and 2,6-dinitro1-benzene-sulfonic acid.

6. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising sodium chr0- mate, a printing paste triazene compound, and a naphthol azo dye coupling component, the improvement comprising steaming the textile in the presence of sodium-3,5- dinitro benzene-sulfonic acid.

7. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising sodium chromate, a printing paste triazene compound, and a naphthol azo dye coupling component, the improvement comprising steaming the textile in the presence of sodium-2,4- dinitroabenzene-sulfonic acid.

8. In a textile printing process comprising applying to the textile a printing paste containing a dye forming composition, said composition comprising sodium chromate, a printing paste triazene compound, and a naphthol azo dye coupling component, the improvement comprising steaming the textile in the presence of sodium 2,6- dinitro-benzene-sulfonic acid.

9. A process for printing a textile with a neutrally developed naphthol azo dye comprising applying to the textile a printing paste which comprises a mixture of an azo dye naphthol coupling component, a triazene formed by action of a diazo compound of a compound taken from the group consisting of para-nitrophenylamines and ortho-nitrophenylamines On a triazene forming component, said latter component :being taken from the class consisting of ortho-nitro-amino benzene compounds and para-nitro-amino benzene compounds, and steaming the textile in the presence of an oxidizing agent and a member of the group consisting of dinitro-benzene-sulfonic acid salts of alkali and alkaline earth metals, the two nitro groups, of Which are on non-adjacent carbon atoms.

10. A printing paste comprising sodium chromate and a dye forming composition comprised of a triazine formed by reacting the diazo compound of a member of the group consisting of S-n-itro-Z-nminotoluol, S-nitro- 2-aminoanisol, and 3-nitro-2aminoanisol with an alkaline salt of a member of the group consisting of an N-loWer alkyl-sulfoanthranilic acid and cyanamide, said dye forming composition (further comprising the ortho-toluidide of beta hydroxy naphthoic acid as coupling component, and a compound of the group consisting of sodium-3,5- dinitro-b enzene-sulfonate, sodium-2,4-dinitro benzenesulfonate, and sodium-2,6-dinitro-4-chloro-benzene-sulfonate.

No references cited. 

1. IN A TEXTILE PRINTING PROCESS COMPRISING APPLYING TO THE TEXTILE A PRINTING PASTE CONTAINING A DYE FORMING COMPOSITION SAID COMPOSITION COMPRISING AN OXIDIZING AGENT, A PRINTING PASTE TRIAZENE COMPOUND, AND A NAPHTHOL COUPLING COMPONENT, THE IMPROVEMENT COMPRISING STEAMING THE TEXTILE IN THE PRESENCE OF A COMPOUND TAKEN FROM THE CLASS CONSISTING OF DINTRO-BENZENE-SULFONIC ACID SALTS OF ALKALI AND ALKALINE EARTH METALS, THE TWO NITRO GROUPS OF WHICH ARE ON NON-ADJACENT CARBON ATOMS. 